Muller-Pritchard-type ((1)J(13C-1H) = a x % s(C)) and related expressions are explored for the prediction, from standard quantum chemical models, of one-bond C-H spin-spin coupling constants, in a series of bi- and polycyclics. Correlations of experimental (1)J(13C-1H) with quantities computed from NBO analyses of PM3 and HF/6-31G* wave functions//geometries are critically examined for 38 aliphatic hydrocarbons (61 distinct tertiary C-H sites; J range >100 Hz). Experimental vs calculated coupling constants are best fit when the model includes contributions from atomic charges (q(H) and q(C)) along with s character at carbon (% s(C)). Previously used geometrical measures of hybridization are also discussed. The relationships obtained can be employed to easily predict one-bond C-H coupling constants at tertiary sites in polycyclic saturated hydrocarbons with experimentally useful accuracy. By using common computational chemistry methods for a large data set, we offer both a predictive tool for the practicing chemist and insights into the validity of hybridization-based interpretations of coupling.